Metal containing polyazo dyestuffs



ue w t fl O METAL CONTAINING PoLYAzo DYESTUFFS Fritz Suckfull, Leverkusen, Rolf Putter, Dusseldorf, and Horst Nickel, Koln-Stammheim, Germany, assignors to Farbenfabriken Bayer Aktieugesellschaft, Leverkusen,

Germany, a corporation of Germany No Drawing. Application August 8, 1956 V Serial No. 602,940 Claims priority, application Germany August 20, 1955 'Clairns. Cl. 260-145) The present invention relates to metal containing polyazo dyestuffs and to a process for their manufacture;

more particularly it relates to metal containing'polyazo dyestuffs .of the following formula H V ,H J M wherein R stands for a radical of an aromatic diazo compound and n means the integer 1 or 2. p

The new metal-containing polyazo dyestuffs are obtainable by coupling in usual manner one side or both sides of the copper complex of the azo compound of the formula If the diazo compounds used contain additional cornplex forminggroups such as the salicylic acid grouping or a complex-forming group in .o-position to the diazo group, the c opper complexes first obtained canbe icon- 2,891,047 Patented June 16, 1959 for the purpose of illustrating the process; they may be replaced by any other diazo component.

The products coupled on both sides can also be produced on the fibre'by first dyeing a dyestuif coupled on one side according to the invention to thefibre and subsequently after-treating the dyeing thus obtained with a diazotized aromatic amine.

The new metal-containing polyazo dyestuifs areparticularly suitable for the dyeing of vegetable fibres such as cotton and regenerated cellulose. In general, green shades are obtained which distinguishthemselves by an outstanding fastne ss to light.

The following examples are given for the purpose of illustrating the invention, Without, however, limiting it thereto; the parts by weight and the parts by volume being in the ratio of grams to millilitres.

Example 1 28.4 parts by weight 0.05 mol) of the copper complex of the azo dyestutf having the formula:

are dissolved in 2400 parts by volume of water and 28 parts by weight of sodium carbonate and combined1 at 0-5" C. with a diazo salt solution prepared from 9.3. parts by weight (0.1 mol) of aniline. When the coupling is completed, the trisazo dyestuff formed is separated by the addition of sodium chloride and isolated. It corresponds in the acid state to the formula H H A fter drying, the dyestutf is a dark powder which dissolves in water with a green coloration. The trisazo dyestulf dyes cotton in green shades of outstanding fastness to light.

Example 2 i 2844 parts by weight (0.05 mol) ofthe copper complex indicated in Example 1 as coupling componentare dissolved in 2400 parts by volume of water and 28 parts by vertedin substance or on thefibrefby the action of metal yielding agents into metal complexes containing more than one complex-combined metal atom molecule.

Diazo components suitable for the present invention are, for example, the following diazotized amines; anilines, o-amino-benzene-carboxylic acids, l-amino-Z- methoxy-benzenes, amines of the naphthalene series, 4- amino-azo-benzene-sulfonic acids, 4-amino-4'nitrostilbene-2,2 disulfonic acids and the like.

The aforesaid diazo components are only mentioned per dyestulf weight of soda and combined with a diazo salt solution prepared from 4.6 parts by weight (0.05 mol) of aniline. The disazo .dyestulf separated with common salt corresponds in the acid state to the formula son:

'and' is after drying a dark powder which dissolves in water with a greenish blue coloration. 'Ihe greenish blue dyeing on cotton changes into a yellowish green upon after-treating on the fibre with a diazotized p-nitroaniline solution.

Example 3 To a one side coupled dyestufi obtained according to the instructions of Example 2 a diazo salt solution is added prepared from 7 parts by weight of l-arninobenzene-Z-carboxylic acid. The trisazo dyestuti formed is separated with sodium chloride and dried. It corresponds in the acid state to the formula It dissol es in water with a green coloration and dyes cotton in green shades.

Example 4 When replacing in Example 1 the aniline by 14 parts by weight (0.1 mol) of 1-amino-benzene-2-carboxylic acid and otherwise proceeding in the same way, a trisazo dyestufi is obtained which corresponds in the acid state to the formula and "dyes cotton in green shades of very good fastness to light,

j The dyein'g's thusobtained can be after-treated on the fibre with copper salts.

Example 5 When replacing in Example l the aniline by 12.3 parts by weight ("0.1 "mol) of o-anisidine and otherwise mQH-N QM proceeding in the same way, a trisazo dyestufi is obtained 'which corresponds 'in the acid state to the formula and dyes cotton in similar shades as the dyestulf obtainable according to Example 1.

' @Qae H=CHQ N=N V 0,11 SOaH i1 4 If the dyestulf obtained according to this example is coppered in substance under de-alkylating conditions, a dyestuif is obtained which dyes cotton a little more bluish.

Example 6 If the aniline is replaced in Example 1 by 17.3 parts by weight (0.1 mol) of o-aminobenzene-sulfonic acid and otherwise the process is carried out in the same way, a very readily water-soluble trisazo dyestutf corresponding in the acid state to the formula 11033 'SOgH N= v -N=N S0311 H 503E is obtained which dyes cotton in similar green shades as the dyestufi obtainable according to Example 1.

Example 7 If 22.5 parts by weight (0.1 mol) of Z-amino-naphthalene-S-sulfonic acid are used in Example 1 instead of aniline, a trisazo dyestuif is formed which, after isolation in usual manner, produces on cotton green shades of very good fastness to light. The dyestufi corresponds in the acid state to the formula Example 8 When replacing in Example 1 the aniline by 30.6 parts by weight (0.1 mol) of N-acetylbenzidine-3'-sulfonic acid and otherwise proceeding in the same way, a trisazo dyestuff is obtained which corresponds in the acid state to the formula sulfonic acid and otherwise proceeding in the same way, a trisazo dyestufi is formed which dyes cotton in 'olive*.

65 green "shades of ver good fastness "to light. The dye-- corresponds in the acid state t the formula QozhonQNo, 05H. 0,1":v

Example 10 wherein each X isahhe m'ber selected from the group con- When replacing in Example 1 the aniline by 27.7 sisting of hydmgen and 8 P, 8

Parts y of f 'f q Q aromatic radical selected from the group consisting of the and otherwise proceeding in the same way, a pentakrsazo dyestuif is obtained which corresponds in the acid state benzene naphthalene lstilbene diphenyl and azobenzene.

to the formula series, at least one X being an --N N-R group. I

Hms- N= sc n no,s-N=N N=N- -N=N N NQ-S 0,11

OH H" l It dyes cotton in green shades. H2 2. metal containing dyestufi of claim lwherein R is Example 11 I a radlcal of the benzene series.

I g l k 3. A metal containing dyestulf of claim 1 wherein R is A solution of Parts y Weight 1 of the r a radical of the naphthalene series. pp Complex described as p n component in 4. A metal containing dyestufi of claim 1 wherein R ample 1, 28 parts by weight of sodium carbonate and 14 i a di l f th tilbe' seri e Parts by Weight of sfldium Y 'QX d in 800 Parts y 5. A dyestufr of claim 1 wherein R contains a metal 111116 of Water and Parts y VQlume Offormamlde 1S complex forming group in o-position to the azo bridge. combined at 0-5" C. with a diazo salt solution prepared 6. A copper-containing dyestufi of the corresponding from 15.4 parts by weight (0.1 mol) of 1-hydroxy-2- for ula amino-4-nitrobenzene. When the coupling is completed, 30 the trisazo dyestufI formed is isolated and dried. It corresponds 1n the acid state to the formula H0as N=N 8 Din O-Ou0 N=N N=NO N10 HOaS =N 5033 DIN Q 0 OH H H 7. A dyestufr selected from the group consisting of OH H6 copper-containing polyazo dyestufis corresponding to the After drying it is a dark powder which dissolves in water formula with a grey coloration. It dyes coton 1n grey shades. The dyeings thus obtained can be after-treated with metalyielding agents, e.g. copper or chromium salts.

HOgS- N=N *SO H Example 12 It 27.2 Parts by weight (0.1 mol) of 1-(4'-aminoben- N=N N=N- zoylamino)-4-hydroxybenzene-3-carboxylic acid are used A in Example 1 instead of aniline and otherwise proceeding 0011 H H H00 in the same way, a trisazo dyestufi is obtained which corresponds in the acid state of the formula and the metal complexes thereof.

0 Ou-O HO S- N=N- 302E It dyes cotton in green shades fast to light. The dyeings possess very good wet-fastness properties and can be aftergzztg metal'yleldmg agents copper or 8. The copper-containing polyazo dyestuif correspond We m ing to the formula 1. A metal-containing polyazo dyestufi corresponding to the general formula 0 Guo 0-Cu-0 2, Asmpper-wntain ng dyestufi of the corresponding formula 10. A copper-containing dyestufi of the corresponding formula V Ems =N so,n HOQNEOCON=N N=N-GO.HNQOH H00 H OH 003 V References Cited in the file of this patent UN ED STATES PATENTS 2,779,756 Riat Jan. 29, 1957 

1. A METAL-CONTAINING POLYAZO DYESTUFF CORRESPONDING TO THE GENERAL FORMULA 